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EP0523109B1 - Hair styling shampoos - Google Patents

Hair styling shampoos Download PDF

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Publication number
EP0523109B1
EP0523109B1 EP91906954A EP91906954A EP0523109B1 EP 0523109 B1 EP0523109 B1 EP 0523109B1 EP 91906954 A EP91906954 A EP 91906954A EP 91906954 A EP91906954 A EP 91906954A EP 0523109 B1 EP0523109 B1 EP 0523109B1
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EP
European Patent Office
Prior art keywords
polymer
vinyl
solvent
hair
weight
Prior art date
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Revoked
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EP91906954A
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German (de)
English (en)
French (fr)
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EP0523109A1 (en
EP0523109A4 (en
Inventor
Robert Lee Wells
Bonnie Theresa King
Michael Albert Snyder
Donald Hugh Frey
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Procter and Gamble Co
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Procter and Gamble Co
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/347—Phenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8135—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers, e.g. vinyl esters (polyvinylacetate)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring

Definitions

  • the present invention relates to hair shampoo compositions which provide not only hair cleaning benefits, but also hair styling benefits. These are achieved by incorporating certain hair styling polymers and solvents for said polymers in a shampoo base.
  • hair conditioning agents can be included in the compositions to provide hair conditioning, cleaning and style hold benefits from a single product.
  • hair care process or product that provides hair styling benefits, especially hair style achievement and hold.
  • the desire to have hair retain a particular shape is widely held.
  • Such style retention is generally accomplished by either of two routes: permanent chemical alteration or temporary alteration of hair style/shape.
  • a temporary alteration is one which can be removed by water or by shampooing.
  • Temporary style alteration has generally been accomplished by means of the application of a third separate composition or compositions to dampened hair after shampooing and/or conditioning.
  • the materials used to provide setting benefits have generally been resins or gums and have been applied in the form of mousses, gels, lotions, or sprays. This approach presents several significant drawbacks to the user. It requires a separate step following shampooing and conditioning to apply the styling composition.
  • the style hold is provided by resin materials which set-up on the hair, the hair tends to feel sticky or stiff after application and it is difficult to restyle the hair without further application of the styling composition.
  • the present invention relates to hair shampoo compositions which comprise surfactants and hair styling agents. Shampooing with these products provides hair cleaning and styling benefits.
  • the present invention relates to shampoo compositions comprising:
  • the shampoo compositions of the present invention contain, as an essential component, a hair styling polymer. It is this component that provides hair styling benefits to the user.
  • a wide variety of hair setting polymers are known for use as styling agents. Many polymers said to be useful in hair styling products are multi-component polymers which combine three, four and even more different monomers into the polymer chains. Frequently, one of the monomer components is vinyl pyrrolidone. Examples of such complex polymer systems are found in U.S. Patent 3,222,329 to Grosser et al., issued December 7, 1965; U.S. Patent 3,577,517 to Kubot et al., issued May 4, 1971; U.S. Patent 4,012,501 to Farber, issued March 15, 1977; U.S. Patent 4,272,511 to Papantoniou and Mondet, issued June 9, 1981; and U.S. Patent 4,196,190, to Gehman et al., issued April 1, 1980.
  • block polymers Other polymers said to be useful for hair styling compositions have been disclosed, such as block polymers. Examples of such block polymer systems are found in U.S. Patent 3,907,984 to Calvert et al., issued September 23, 1975; U.S. Patent 4,030,512 to Papantoniou et al., issued June 21, 1977; and U.S. Patent 4,283,384 to Jacquet et al., issued August 11, 1981.
  • the styling polymers of the present invention are of relatively low water-solubility. More specifically, these polymers have a solubility parameter, ⁇ , of between about 17.4 and about 24.5 ( ⁇ units equal (Joule/cm 3 ) 1/2 ), preferably from about 19.4 to about 23.5, most preferably from about 22.5 to about 23.5 (Joule/cm 3 ) 1/2 . (about 8.5 and about 12.0 ( ⁇ units equal (cal/cm 3 ) 1/2 ), preferably from about 9.5 to about 11.5, most preferably from about 11 to about 11.5.)
  • solubility parameter is defined in the Polymer Handbook 3rd Ed. (John Wiley and Sons, New York), J. Brandrup and E.H. Immergut, Chapter VII, pp. 519-559, as the square root of the cohesive energy density and describes the attractive strength between molecules of the material. Solubility parameters may be determined by direct measurement, correlations with other physical properties, or indirect calculation. The solubility parameters of the present polymers were determined by indirect calculations of group contributions as described in section 2.3 on p. 524-526 of the cited reference.
  • styling polymers having water solubilities within this range can be dispersed with the polymer solvent, as described infra , in shampoo compositions as a dispersed fluid phase. Formulation in this way has been shown to provide maximum deposition of styling polymer out of the shampoo composition and onto hair. Styling polymers having solubility parameters at the upper end of this range would be soluble by themselves in the present shampoo compositions. It has now been found that when these polymers are combined with the polymer solvents of the present invention (as defined infra ) and then dispersed in the shampoo composition, they remain in the composition as a dispersed fluid phase.
  • Polymers having solubility parameters greater than about 24.5 (12.0) will themselves be solubilized in the shampoo composition (even when they are pre-mixed with the present polymer solvents) preventing optimum deposition of polymer on hair. Styling polymers having solubility parameters lower than about 17.4 (8.5) will not deposit effectively from the shampoo.
  • the present styling polymers must comprise at least one polymerizable hydrophobic monomer.
  • the polymer may be a homopolymer or a copolymer of hydrophobic monomers.
  • the present styling polymers may be a copolymer of a hydrophilic monomer and a hydrophobic monomer, or mixtures thereof.
  • the present hair styling polymers comprise from 0% to about 30% of a polymerizable hydrophilic monomer (M A ) or mixtures thereof, and from about 70% to about 100% of a polymerizable hydrophobic monomer (M B ), or mixtures thereof.
  • M A polymerizable hydrophilic monomer
  • M B polymerizable hydrophobic monomer
  • the styling polymer comprises both M A monomer and M B monomer, then the monomers must be copolymerizable with each other.
  • % M A ( ⁇ s - 6.7) x 5.56 ⁇ 10 wherein M A is the hydrophilic monomer and ⁇ s is the solubility parameter of the polymer solvent component (as described infra ). (If % M A is calculated as less than zero, then no hydrophilic monomer is included in the copolymer).
  • % M A ( ⁇ s - 6.7) x 5.56 ⁇ 3.
  • Preferred hydrophilic monomers of the present styling polymers include acrylic acid, methacrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, methacrylamide, N-t-butyl acrylamide, maleic acid, maleic anhydride and its half esters, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, vinyl pyrrolidone, vinyl ethers (such as methyl vinyl ether), maleimides, vinyl pyridine, vinyl imidazole, other polar vinyl heterocyclics, styrene sulfonate, allyl alcohol, vinyl alcohol (produced by the hydrolysis of vinyl acetate after polymerization), vinyl caprolactam, and mixtures thereof.
  • Preferred hydrophobic monomers include acrylic or methacrylic acid esters of C 1 -C 18 alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, t-butanol, cyclohexanol, neodecanol, 2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decano
  • Optimum performance of the present hair styling polymers in terms of style hold has been found when the weight average molecular weight of the styling polymer is between about 5,000 and about 1,000,000, preferably between about 10,000 and about 100,000, and the glass transition temperature, Tg, (i.e., the temperature at which the polymer changes from a brittle vitreous state to a plastic state) of the styling polymer is greater than about -20°C, preferably between about 0°C and about 80°C, and most preferably between about 20°C and about 60°C.
  • Tg glass transition temperature
  • Specific styling polymers of the present invention which have been found to provide the desired deposition/styling benefits out of a shampoo system are as follows: vinyl pyrrolidone/vinyl acetate copolymers (at ratios of up to about 30%, by weight, vinyl pyrrolidone); vinyl acetate homopolymer; t-butyl acrylate homopolymer; t-butyl styrene/ ethyl hexyl methacrylate copolymer (50/50, by weight); dimethyl acrylamide/ t-butyl acrylate/ethyl hexyl methacrylate copolymer (10/45/45); ethylene/vinyl acetate copolymer (12.5/87.5); allyl alcohol/styrene copolymer (19/81); vinyl chloride/vinyl acetate copolymer (83/17 and lower); vinyl pyrrolidone/vinyl acetate/butyl acrylate copoly
  • the polymer styling agent is present in the compositions of the present invention at a level of from about 0.2% to about 20%, preferably at a level of from about 2% to about 6%. At levels below about 0.2% styling polymer, the present hair style hold benefits cannot be achieved; at levels above about 20% styling polymer, interference with shampoo in-use characteristics may occur.
  • the styling polymers of the present invention formulated in the present shampoo compositions provide hair styling benefits. Such beneifts include ease of style achievement and style maintenance.
  • the present compositions also provide some degree of restyling benefits. That is, after the hair is shampooed with the present compositions and styled, the hair "remembers" the style after being subjected to a force, such as combing, brushing or simply flattening of the hair.
  • a second essential component of the present shampoo compositions is a solvent or diluent for the styling polymer.
  • the solvent is necessary for dilution of the polymer so that it can be dispersed in the shampoo composition.
  • the solvent also aids in delivering style achievement by making polymer deposited on the hair more tacky through the hair drying and styling process.
  • the polymer solvent must have a low solubility in water, comparable with the water solubility of the polymer.
  • the particular polymer chosen for use in the present shampoo compositions must be soluble in the particular solvent utilized. This enables the dispersion of the polymer/solvent mixture as a dispersed fluid phase in the shampoo composition and maintenance of that dispersed second phase.
  • the polymer solvents of the present invention have a solubility parameter, ⁇ s , of between about 14.3 and about 25.6, preferably between about 16.4 and about 20.5 (Joule/cm 3 ) 1/2 (about 7 and about 12.5, preferably between about 8 and about 10).
  • the solubility parameters of solvents are usually determined by direct measurement. Values for ⁇ s for the solvents of the present invention in (cal/cm 3 ) 1/2 ) were taken from Table 3.1 and 3.2 in the Polymer Handbook reference cited above. The upper end of this solubility range covers solvent materials which, if dispersed in the shampoo base alone, would be soluble. However, it has been found that when these solvents are premixed with the polymers of the present invention, prior to dispersion in the shampoo composition, they will remain in the polymer phase, i.e., unsolubilized in the shampoo base.
  • the polymer solvent must also be volatile. Upon deposition of the polymer/solvent mixture on the hair, the solvent is volatilized leaving only the styling polymer on the hair, thus providing the maximum styling benefits.
  • the polymer solvents of the present invention have a boiling point of less than or equal to about 300°C.
  • the polymer solvent must not interact with the polymer styling agent in such a way that would substantially reduce the ability of the polymer to provide styling benefits to hair under ordinary use situations.
  • the solvents must, of course, be of sufficiently high purity and sufficiently low toxicity to render them suitable for administration to human hair.
  • Specific polymer solvent materials that have been found to be useful in the present invention include isopropanol, butyl alcohol, amyl alcohol, phenyl ethanol, benzyl alcohol, phenyl propanol, ethyl butyrate, isopropyl butyrate, diethyl phthalate, phenyl ethyl dimethyl carbinol, ethyl-6-acetoxyhexanoate, and methyl(2-pentanyl-3-oxy)cyclopentylacetate, and mixtures thereof.
  • Preferred solvents for use herein are diethyl phthalate, phenyl ethyl dimethyl carbinol, ethyl-6-acetoxyhexanoate, and mixtures thereof.
  • the amount of solvent to be used in the present shampoo compositions is an amount sufficient to solubilize the polymer and disperse it as a separate fluid phase in the shampoo composition. Generally, from about 0.2% to about 20%, preferably from about 2% to about 6%, polymer solvent is used. At levels below about 0.2% solvent, the polymer cannot be sufficiently diluted; at levels above about 20% solvent, shampoo in-use characteristics may be negatively affected.
  • the ratio of polymer to solvent in the present composition is from about 10:90 to about 80:20, preferably from about 40:60 to about 60:40.
  • EPO Patent Publication 0323715 teaches polymer and solvent systems having very low water solubilities (polymer is less than 0.1% soluble in water, diluent is less than 0.2% soluble in water) which are dispersed as a separate fluid phase in hair care compositions. Polymer/solvent systems having such low water solubilities have been found to interfere with the present shampoo in-use characteristics, namely lathering.
  • the surfactant comprises from about 5% to about 30% by weight, preferably from about 12% to about 25%, of the shampoo composition.
  • a wide variety of surfactant materials may be utilized including anionic, nonionic, zwitterionic and amphoteric surfactants.
  • Synthetic anionic detergents useful herein include alkyl and alkyl ether sulfates. These materials have the respective formulae ROSO 3 M and RO(C 2 H 4 O) x SO 3 M, wherein R is alkyl or alkenyl of from about 8 to about 20 carbon atoms, x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium and triethanolamine.
  • the alkyl ether sulfates useful in the present invention are condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 20 carbon atoms.
  • R has from about 12 to about 18 carbon atoms in both the alkyl and alkyl ether sulfates.
  • the alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred herein. Such alcohols are reacted with about 1 to about 10, and especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
  • alkyl ether sulfates which may be used in the present invention are sodium coconut alkyl triethylene glycol ether sulfate; sodium tallow alkyl triethylene glycol ether sulfate; and sodium tallow alkyl hexaoxyethylene sulfate.
  • Highly preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from about 12 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide.
  • Such a mixture also comprises from about 0 to about 20% by weight C 12-13 compounds; from about 60 to about 100% by weight of C 14-15-16 compounds, from about 0 to about 20% by weight of C 17-18-19 compounds; from about 3 to about 30% by weight of compounds having a degree of ethoxylation of 0; from about 45 to about 90% by weight of compounds having a degree of ethoxylation of from about 1 to about 4; from about 10 to about 25% by weight of compounds having a degree of ethoxylation of from about 4 to about 8; and from about 0.1 to about 15% by weight of compounds having a degree of ethoxylation greater than about 8.
  • R 1 -SO 3 -M Another suitable class of anionic surfactants are the water-soluble salts of the organic, sulfuric acid reaction products of the general formula: R 1 -SO 3 -M wherein R 1 is chosen from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 12 to about 18, carbon atoms; and M is a cation.
  • salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series including iso-, neo-, ineso-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., SO 3 , H 2 SO 4 , oleum, obtained according to known sulfonation methods, including bleaching and hydrolysis.
  • a sulfonating agent e.g., SO 3 , H 2 SO 4 , oleum
  • anionic synthetic surfactants which come within the terms of the present invention are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil.
  • Other anionic synthetic surfactants of this variety are set forth in U.S. Patents 2,486,921; 2,486,922; and 2,396,278.
  • Still other anionic synthetic surfactants include the class designated as succinamates.
  • This class includes such surface active agents as disodium N-octadecylsulfosuccinamate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.
  • olefin sulfonates having about 12 to about 24 carbon atoms.
  • olefin sulfonates is used herein to mean compounds which can be produced by the sulfonation of ⁇ -olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates.
  • the sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO 2 , chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO 2 , etc., when used in the gaseous form.
  • inert diluents for example by liquid SO 2 , chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO 2 , etc., when used in the gaseous form.
  • the ⁇ -olefins from which the olefin sulfonates are derived are mono-olefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. Preferably, they are straight chain olefins.
  • suitable 1-olefins include 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosene.
  • the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
  • anionic organic surfactants are the ⁇ -alkyloxy alkane sulfonates. These compounds have the following formula: where R 1 is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R 2 is a lower alkyl group having from about 1 (preferred) to about 3 carbon atoms, and M is a water-soluble cation as hereinbefore described.
  • ⁇ -alkyloxy-alkane-1-sulfonates or alternatively 2-alkyloxy-alkane-1-sulfonates, having low hardness (calcium ion) sensitivity useful herein include: potassium- ⁇ -methoxydecanesulfonate, sodium 2-methoxy-tridecanesulfonate, potassium 2-ethoxytetradecylsulfonate, sodium 2-isopropoxyhexadecylsulfonate, lithium 2-t-butoxytetradecyl-sulfonate, sodium ⁇ -methoxyoctadecylsulfonate, and ammonium ⁇ -n-propoxydodecylsulfonate.
  • Nonionic surfactants which are preferably used in combination with an anionic, amphoteric or zwitterionic surfactant, can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Examples of preferred classes of nonionic surfactants are:
  • dimethicone copolyols useful herein, include Silwet Surface Active Copolymers (manufactured by the Union Carbide Corporation); Dow Corning Silicone Surfactants (manufactured by the Dow Corning Corporation); Silicone Copolymer F-754 (manufactured by SWS Silicones Corp.); and Rhodorsil 70646 Fluid (manufactured by Rhone Poulenc, Inc.).
  • Zwitterionic surfactants are exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • R 2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety;
  • Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms;
  • R 3 is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms;
  • X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus atom;
  • R 4 is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
  • surfactants examples include:
  • betaines are also useful in the present invention.
  • betaines useful herein include the high alkyl betaines, such as coco dimethyl carboxymethyl betaine, cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, and lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine.
  • the sulfobetaines may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine and the like; amidobetaines and amidosulfobetaines, wherein the RCONH(CH 2 ) 3 radical is attached to the nitrogen atom of the betaine are also useful in this invention.
  • Preferred betaines for use in the present compositions are cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, and oleyl betaine.
  • amphoteric surfactants which can be used in the compositions of the present invention are those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • an anionic water solubilizing group e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Examples of compounds falling within this definition are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylamino-propane sulfonate, sodium lauryl sarcosinate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Patent 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Patent 2,438,091, and the products sold under the trade name "Miranol" and described in U.S. Patent 2,528,378.
  • surfactants can be used alone or in combination in the hair care compositions of the present invention.
  • Preferred surfactants for use in the present shampoo compositions include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine
  • the most preferred shampoos of the present invention contain specific combinations of anionic surfactants, zwitterionic surfactants, and amphoteric surfactants.
  • the preferred shampoos contain from about 2% to about 10% of a betaine, such as cocoamidopropyl betaine; from about 2% to about 16% of alkyl sulfates and alkyl ethoxylated sulfates, preferably from about 2% to about 6% alkyl sulfates and from 0% to about 14% of ethoxylated alkyl sulfates; and from 0% to about 8% of sarcosinates such as sodium lauroyl sarcosinate, with a total surfactant level of from about 15% to about 20%.
  • a betaine such as cocoamidopropyl betaine
  • alkyl sulfates and alkyl ethoxylated sulfates preferably from about 2% to about 6% alkyl sulfates and from 0%
  • the combination of betaine and alkyl sulfates and/or alkyl ethoxylated sulfates builds viscosity of the shampoo composition and increases lather upon use.
  • the sarcosinate controls viscosity without decreasing lather and also aids in deposition of the styling agent.
  • this surfactant combination when used in a shampoo containing the preferred solvents of the present invention, gives optimum composition viscosity, in-use lather, and styling agent deposition.
  • the shampoo compositions of the present invention also preferably comprise a hair conditioning agent. It is this agent that provides hair conditioning benefits such as ease of combing, soft hair feel, and manageability to the user.
  • the resulting shampoo composition provides hair cleaning, styling and conditioning benefits in one product.
  • Cationic surfactants as described previously, can be used to give some conditioning benefits in the present compositions.
  • protein derivatives such as hydrolyzed animal proteins, for example, Crotein SPA (Croda) or Lexeine X250 (Inolex) or Polypeptide LSN (Stephan), can be used to provide conditioning benefits.
  • the hair conditioning agent of the present invention is a siloxane or a siloxane-containing material and is present at a level of from about 0.01% to about 10% of the shampoo composition, preferably from about 0.1% to about 5%, most preferably from about 0.2% to about 3%.
  • Siloxanes see, for example, U.S. Patent 3,208,911, Oppliger, issued September 28, 1965
  • siloxane-containing polymers have been taught for use in hair conditioning compositions.
  • U.S. Patent 4,601,902, Fridd et al ., issued July 22, 1986 describes hair conditioning or shampoo/conditioner compositions which include a polydiorganosiloxane having quaternary ammonium substituted groups attached to the silicon, and a polydiorganosiloxane having silicon-bonded substituents which are amino-substituted hydrocarbon groups.
  • Patent 4,654,161 Kollmeier et al., issued March 31, 1987, describes a group of organopolysiloxanes containing betaine substituents. When used in hair care compositions, these compounds are said to provide good conditioning, compatibility with anionic components, hair substantivity, and low skin irritation.
  • U.S. Patent 4,563,347, Starch, issued January 7, 1986 relates to hair conditioning compositions which include siloxane components containing substituents to provide attachment to hair.
  • Japanese Published Application 56-129,300, Lion Corporation published October 9, 1981, relates to shampoo conditioner compositions which include an organopolysiloxaneoxyalkylene copolymer together with an acrylic resin.
  • a silicon derivative e.g., polyether- or alcohol-modified siloxanes.
  • Polyether-modified polysiloxanes are also disclosed for use in shampoos in U.S. Patent 3,957,970, Korkis, issued May 18, 1976.
  • Siloxane-derived materials have also been used in hair styling compositions.
  • Japanese Published Application 56-092,811, Lion Corporation, published December 27, 1979 describes hair setting compositions which comprise an amphoteric acrylic resin, a polyoxyalkylene-denatured organopolysiloxane, and polyethylene glycol.
  • U.S. Patent 4,744,978, Homan et al., issued May 17, 1988 describes hair styling compositions (such as hair sprays) which include the combination of a carboxyfunctional polydimethylsiloxane and a cationic organic polymer containing amine or ammonium groups. Hair styling compositions which include polydiorganosiloxanes and a cationic organic polymer are taught in U.S.
  • Patent 4,733,677 Gee et al., issued March 29, 1988
  • U.S. Patent 4,724,851 Cornwall et al., issued February 16, 1988.
  • European Patent Application 117,360, Cantrell et al., published September 5, 1984 discloses compositions, containing a siloxane polymer having at least one nitrogen-hydrogen bond, a surfactant, and a solubilized titanate, zirconate or germanate, which act as both a conditioner and a hair styling aid.
  • Nonvolatile silicone fluids are useful as the conditioning agent component in the shampoo compositions of the present invention.
  • examples of such materials include polydimethylsiloxane gums, aminosilicones and phenylsilicones. More specifically, materials such as polyalkyl or polyaryl siloxanes with the following structure: wherein R is alkyl or aryl, and x is an integer from about 7 to about 8,000 may be used.
  • A represents groups which block the ends of the silicone chains.
  • the alkyl or aryl groups substituted on the siloxane chain (R) or at the ends of the siloxane chains (A) may have any structure as long as the resulting silicones remain fluid at room temperature, are hydrophobic, are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the composition, are chemically stable under normal use and storage conditions, and are capable of being deposited on and of conditioning hair.
  • Suitable A groups include methyl, methoxy, ethoxy, propoxy, and aryloxy.
  • the two R groups on the silicone atom may represent the same group or different groups. Preferably, the two R groups represent the same group.
  • Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl.
  • the preferred silicones are polydimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred.
  • Suitable methods for preparing these silicone materials are disclosed in U.S. Patents 2,826,551 and 3,964,500 and references cited therein. Silicones useful in the present invention are also commercially available. Suitable examples include Viscasil, a trademark of the General Electric Company and silicones offered by Dow Corning Corporation and by SWS Silicones, a division of Stauffer Chemical Company.
  • silicone conditioning materials include materials of the formula: in which x and y are integers which depend on the molecular weight, the average molecular weight being approximately between 5,000 and 10,000. This polymer is also known as "amodimethicone”.
  • silicone cationic polymer conditioning agents which can be used In the present compositions correspond to the formula: (R 1 ) a G 3-a -Si-(-OSiG 2 ) n -(OSiG b (R 1 ) 2-b ) m -O-SiG 3-a (R 1 ) a in which G is chosen from the group consisting of hydrogen, phenyl, OH, C 1 -C 8 alkyl and preferably methyl; a denotes 0 or an integer from 1 to 3, and preferably equals 0;
  • silicone cationic polymer conditioning agents which can be used In the present compositions correspond to the formula: in which R 3 denotes a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and more especially an alkyl or alkenyl radical such as methyl;
  • a polymer of this class which is especially preferred is that sold by UNION CARBIDE under the name "UCAR SILICONE ALE 56".
  • Conditioning agent materials also useful in the compositions of the present invention are silicone polymer materials which provide both style retention and conditioning benefits to the hair. These materials comprise rigid silicone polymers.
  • Such materials include, but are not limited to, filler reinforced polydimethyl siloxane gums including those having end groups such as hydroxyl; cross linked siloxanes, such as organic substituted silicone elastomers; organic substituted siloxane gums, including those having end groups such as hydroxyl; and resin reinforced siloxanes.
  • the rigid silicone polymers useful in the present invention have complex viscosities of at least 2 x 10 5 poise (P), preferably about 1 x 10 7 poise, where complex viscosity is measured by subjecting a sample to oscillatory shear at a fixed frequency of 0.1 rad/sec at 25°C using a Rheometric Fluids Spectrometer® measuring films having a thickness of about 1 millimeter. The resulting viscous and elastic force responses are combined to determine the complex modulus which is divided by the imposed frequency to compute the complex viscosity.
  • a preferred siloxane gum useful in the present invention is a diphenyl-dimethyl polysiloxane gum having a molecular weight of at least about 500,000, and must be diphenyl substituted to the extent of 3% or more, preferably at least about 5%.
  • the siloxane gums may also be filler reinforced to provide additional rigidity.
  • Silica is the preferred filler.
  • Such reinforced guns comprise up to about 15-20% silica.
  • Silicone resins also useful in formulating the rigid silicones in the present compositions are silicone polymers with a high degree of crosslinking introduced through the use of trifunctional and tetrafunctional silanes.
  • Typical silanes used in the manufacture of resins are monomethyl, dimethyl, monophenyl, diphenyl, methylphenyl, monovinyl, and methylvinyl chlorosilanes, together with tetrachlorosilane.
  • a preferred resin is one offered by General Electric as GE SR545. This resin is provided as a solution in toluene which is stripped prior to the resin's use. This resin is used in combination with the siloxane gum to provide extra rigidity.
  • rigid silicone polymers of use herein are those siloxanes which have been sparingly crosslinked but are still soluble in solvents such as cyclomethicone.
  • Precursors for the rigid material can be any high molecular weight polydimethyl siloxanes, polydimethyl siloxanes containing vinyl groups and other siloxanes.
  • Methods of crosslinking include heat curing with organic peroxides such as dibenzoyl peroxide and di-t-butyl peroxide, heat vulcanization with sulfur, and high-energy radiation.
  • the silicone conditioning agent should be selected such that it does not interfere with the shampoo cleaning and hair style holding performance.
  • the silicone conditioning agent comprises a polydimethylsiloxane gum, having a viscosity greater than about 1,000,000 mPas -1 (centipoise) and a dimethicone fluid having a viscosity of from about 10 mPas -1 (centipoise) to about 100,000 mPas -1 (centipoise) wherein the ratio of gum to fluid is from about 30:70 to about 70:30, preferably from about 40:60 to about 60:40.
  • the hair styling agent and hair conditioning agent of the present compositions can be provided by a single material.
  • such materials are copolymers having siloxane macromers grafted thereto, which meet the functional limitations as defined supra . That is, the non-silicone backbone of such polymers should have a molecular weight of from about 5,000 to about 1,000,000, a Tg of greater than about -20°C, and a solubility parameter of from about 8.5 to about 12.0.
  • Preferred polymers comprise a polymeric backbone and, grafted to the backbone, a polydimethylsiloxane macromer having a weight average molecular weight of from about 1,000 to about 50,000, preferably from about 5,000 to about 40,000, most preferably about 10,000.
  • the polymer is such that when it is formulated into the finished hair care composition used to treat the hair, and then the hair dried, the polymer phase separates into a discontinuous phase which includes the polydimethylsiloxane macromer and a continuous phase which includes the backbone. It is believed that this phase separation property provides a specific orientation of the polymer on hair which results in the desired hair conditioning and setting benefits.
  • the copolymers comprise C monomers together with monomers selected from the group consisting of A monomers, B monomers, and mixtures thereof. These copolymers contain at least A or B monomers together with C monomers, and preferred copolymers contain A, B and C monomers.
  • copolymers are comprised of monomers A, C and, optionally, B, which are defined as follows.
  • A is at least one free radically polymerizable vinyl monomer or monomers.
  • B when used, comprises at least one monomer copolymerizable with A.
  • B may be up to about 30%, preferably up to about 10%, more preferably 5%, of the total monomers in the copolymer.
  • Monomer C comprises from about 0.01% to about 50.0% of the total monomers in the copolymer.
  • a monomers are the same as the hydrophobic monomers described supra for the styling polymers of the present invention which do not comprise siloxane macromers.
  • B monomers are the same as the hydrophilic monomers described supra for the styling polymers of the present invention which do not comprise siloxane macromers.
  • the C monomer has the general formula: X(Y) n Si(R) 3-m Z m wherein X is a vinyl group copolymerizable with the A and B monomers; Y is a divalent linking group; R is a hydrogen, lower alkyl, aryl or alkoxy; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, is essentially unreactive under copolymerization conditions and is pendant from the vinyl polymeric backbone, described above; n is 0 or 1; and m is an integer from 1 to 3.
  • C has a weight average molecular weight of from about 1,000 to about 50,000, preferably from about 5,000 to about 40,000, most preferably about 10,000.
  • the C monomer has a formula selected from the following group: X-Si(R 4 ) 3-m Z m and
  • siloxane containing copolymers generally comprise from 50% to about 98% (preferably from about 85% to about 98%, more preferably from about 90% to about 97%) of monomer A, from 0% to about 30% (preferably from about 2% to about 8%) of monomer B, and from about 0.1% to about 50% (preferably from about 0.5% to about 20%, most preferably from about 2% to about 10%) of monomer C.
  • the combination of the A and B monomers preferably comprises from about 50.0% to about 99.9% (more preferably about 80% to about 99%, most preferably from about 90% to about 98%) of the polymer.
  • polymers which may be used in the present invention include the following (the weight percents below refer to the amount of reactants added in the polymerization reaction, not necessarily the amount in the finished polymer):
  • the present copolymers must be diluted with a polymer solvent of the present invention prior to combination with the remaining shampoo composition ingredients. This will enable the formation of a separate dispersed phase of polymer and solvent in the shampoo composition.
  • siloxane-containing copolymers When used in the shampoo compositions of the present invention, to act as both a hair styling polymer and hair conditioning agent, they are generally present at a level of from about 0.2% to about 20%, preferably from about 2% to about 6%.
  • these materials which act as both the hair styling polymer and hair conditioning agent in the present compositions comprise a polyvinyl pyrrolidone/polydimethyl siloxane/vinyl acetate copolymer wherein the non-silicone backbone of the copolymer has a molecular weight of from about 10,000 to about 100,000, a T g of from about 20°C to about 60°C, and a solubility parameter, ⁇ , of from about 22.5 to about 23.5 (Joule/cm 3 ) 1/2 (about 11.0 to about 11.5 (cal/cm 3 ) 1/2 )
  • the hair care compositions herein can contain a variety of other optional components suitable for rendering such compositions more cosmetically or aesthetically acceptable or to provide them with additional usage benefits.
  • Such conventional optional ingredients are well-known to those skilled in the art, e.g., pearlescent aids, such as TiO 2 coated mica, ethylene glycol distearate, and PEG 3 distearate; opacifiers; preservatives, such as benzyl alcohol, Glydant, Kathon, methyl paraben, propyl paraben and imidazolidinyl urea; fatty alcohols, such as cetearyl alcohol; sodium chloride; sodium sulfate; polyvinyl alcohol; ethyl alcohol; pH adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, monosodium phosphate, disodium phosphate, sodium hydroxide, and sodium carbonate; coloring agents, such as any of the FD&C or D&C dyes; perfumes; sequest
  • compositions can also optionally comprise thickeners and viscosity modifiers, such as a diethanolamide of a long chain fatty acid (e.g, PEG 3 lauric diethanolamide), lauramide DEA, cocomonoethanol amide, dimethicone copolyols, guar gum, xanthan gum, methyl cellulose, hydroxyethyl cellulose, starches and starch derivatives.
  • the compositions may comprise a nonionic long chain alkylated cellulose ether thickener such as those materials described in U.S. Patent 4,228,277, Landoll, issued October 14, 1980.
  • Such optional ingredients generally are used individually at levels of from about 0.01% to about 10.0%, preferably from about 0.05% to about 5.0%, of the shampoo composition.
  • the present invention should not contain optional components which unduly interfere with the cleaning and hair style holding performance of the present shampoo compositions.
  • the balance of the present shampoo compositions comprises water or water combined with some other carrier substance which does not interfere with the cleaning/conditioning/style hold benefits of the present compositions.
  • the hair care compositions of the present invention can be made using conventional formulation and mixing techniques.
  • the polymer must first be dissolved in the polymer solvent.
  • the remaining ingredients are combined in a separate vessel and the polymer/solvent mixture is added.
  • the hair care compositions of the present invention are used in conventional ways to provide the hair cleaning/conditioning/ styling hold benefits of the present invention.
  • Such method generally involves application of an effective amount of the shampoo product to the hair, which is massaged through and then rinsed from the hair.
  • effective amount is meant an amount sufficient to provide the hair cleaning/conditioning/styling hold benefits desired considering the length and texture of the hair.
  • This product is prepared by first dissolving the polyvinylpyrrolidone/vinyl acetate (5/95) copolymer in the phenyl ethyl dimethyl carbinol. The remaining components are combined in a separate vessel with heating and stirring to melt the solids. The polymer/solvent mixture is then added to the remaining components either hot or after they have been cooled.
  • This shampoo product provides hair cleaning benefits as well as hair conditioning and hair style holding benefits.
  • This product is prepared using the method described in Example I.
  • This shampoo product provides hair cleaning benefits as well as hair conditioning and hair style holding benefits.
  • This product is prepared using the method described in Example I.
  • This shampoo product provides hair cleaning benefits as well as hair conditioning and hair style holding benefits.
  • This product is prepared using the method described in Example I.
  • This shampoo product provides hair cleaning benefits as well as hair conditioning and hair style holding benefits.
  • This product is prepared using the method described in Example I.
  • This shampoo product provides hair cleaning benefits as well as hair conditioning and hair style holding benefits.

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NO924798L (no) 1992-12-11
ATE161417T1 (de) 1998-01-15
CA2079680A1 (en) 1991-10-07
AU7661891A (en) 1991-10-30
FI924473L (fi) 1992-10-05
CS97491A3 (en) 1992-02-19
WO1991015185A1 (en) 1991-10-17
EP0523109A1 (en) 1993-01-20
IE911139A1 (en) 1991-10-09
EP0523109A4 (en) 1993-10-27
NO924798D0 (no) 1992-12-11
TW199864B (fi) 1993-02-11
TR26319A (tr) 1995-03-15
PT97273A (pt) 1991-12-31
CN1056416A (zh) 1991-11-27
FI924473A0 (fi) 1992-10-05
BR9106318A (pt) 1993-04-20
JP3247107B2 (ja) 2002-01-15
ES2110992T3 (es) 1998-03-01
DE69128529T2 (de) 1998-07-30
JPH05508389A (ja) 1993-11-25
AR247482A1 (es) 1995-01-31
MA22116A1 (fr) 1991-12-31
US5120532A (en) 1992-06-09
HU9202956D0 (en) 1992-11-30
DE69128529D1 (de) 1998-02-05
CA2079680C (en) 1997-02-25
CN1065127C (zh) 2001-05-02
HUT62450A (en) 1993-05-28

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